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In studying photovoltaic devices made with silicon thin films and considering them according to their grain size, it is curious that as the crystalline fraction increases, the open-circuit voltage (Voc) – rather than approaching that of the single-crystal case – shows a decline. To gain an insight into this behavior, observed in hydrogenated microcrystalline silicon (μc-Si:H) solar cells prepared under a variety of deposition conditions, we have used a detailed electrical-optical computer modeling program, ASDMP. Two typical μc-Si:H cells with low (~79%) and higher (~93%) crystalline volume fractions (Fc), deposited in our laboratory and showing this general trend, were modeled. From the parameters extracted by simulation of their experimental current density – voltage and quantum efficiency characteristics, it was inferred that the higher Fc cell has both a higher band gap defect density as well as a lower band gap energy. Our calculations reveal that the proximity of the quasi-Fermi levels to the energy bands in cells based on highly crystallized μc-Si:H (assumed to have a lower band gap), results in both higher free and trapped carrier densities. The trapped hole population, that is particularly high near the P/I interface, results in a strong interface field, a collapse of the field in the volume, and hence a lower open-circuit voltage. Interestingly enough, we were able to fabricate fluorinated μc-Si:H:F cells having 100% crystalline fraction as well as very large grains, that violate the general trend and show a higher Voc. Modeling indicates that this is possible for the latter case, as also for a crystalline silicon PN cell, in spite of a sharply reduced band gap, because the lower effective density of states at the band edges and a sharply reduced gap defect density overcome the effect of the lower band gap

Factors limiting the open-circuit voltage in microcrystalline silicon solar cells